Method of printing and article resulting therefrom



April 16, 1935'. e. A. FLETCHER 1,997,769

METHOD OF PRINTING AND ARTICLE RES ULTING THEREFROM' I F ile d Oct. 8,1952 lil lid

Patented Apr. 16, 1935 A v UNITED STATES PATENT OFFICE i METHOD OFPRINTING AND ARTICLE RESULTING THEREFROM Application October 8,1932,Serial No. 636,813

26 Claims.

This invention relates to printing wet materials. More particularly,this invention relates to the printing of pellicular materials such asregenerated cellui se articles, such as caps, bands, sheets or the like,in the gel state.

At the present time, caps and bands of regenerated cellulose areextensively employed as protective covers for numerous articles or for.similar purposes. These materials, according to one process, are made bycoating a form of the desired contour with a cellulosic solution, suchas a viscose solution, for example, by immersing an appropriately shapedmandrel into the desired solution, and, after withdrawing the mandrel,coagulating the viscose solution adhering thereto. The coagulatedmaterial is,'preferably after removal from the mandrel, subjected to aregenerating bath. Subsequently, the regenerated cellulose article issubjected to the usual purifying operations, such as desulphuring andbleaching, and finally washed. At the end of these operations, theproduct is in the gel state, in which condition it is-maintained, as bybeing kept submerged in water, with or without the addition of apreservative, until it is applied to the object. The cap or band isapplied to the article while in the gel state and, during drying, itshrinks to a considerable extent and intimately conforms to the objectcovered, resuiting in a covering which is-smooth, tight and neat inappearance.

The caps or bands may be plain and transparent or colored andtransparent. When colored transparent materials are desired, anappropriate dyestufi is incorporated in the molding solution. cAlternatively, plain and transparent caps or bandsmay be dyed. If theyare to be opaque and of any desired color, this is secured byincorporating in the molding solution a pigment of the desired color.When caps or bands having a metallic appearance are desired, this issecured by incorporating a suitable material, such as ground mica, inthe viscose. In this way various color schemes maybe chosen to designatecertain types of merchandise. Inasmuch as the uses of these caps orhands are so widely diversified, it is highly desirable that someadditional identifying indicia be provided thereon, as by printing,without impairing the product and preferably also without any modifyingei'iect on the procedure for applying them.

The caps or bands in the gel state cannot be I satisfactorily printedaccording to the present day printing processes. Due to the wetcondition of the material, when the ink is applied thereto, it

will not readily dry and will moreover run, smear or otherwise bedefaced.

Dry caps or bands of regenerated cellulose may be printed in any one ofthe common and well known manners. However, when such processes areused, the surface which is to receive the printing must be flat. This isnot always possible when the caps or bands are applied and shrunk inposition since, as previously explained, they intimately conform to theshape and contour of the article on which they are disposed. Even ifthis procedure were satisfactory, it Would nevertheless be uneconomicalfrom the users point of view. He would have to apply the cap or band,permit it to dry in place and then, if possible,

usual printing process while in the dry state and then subsequentlywetted or swollen prior to application, the printing is apt to smear orrub oif or be otherwise defaced, since it is only on the surface of thecellulose.

I have found that I can overcome the abovementioned undesirable featuresby printing wet pellicular materials, such as regenerated cellulosearticles, in the gel state, by dyeing the material in accordance withany desired indicia, as by forming in situ a substantially permanentcoloring, such as a. dyestufl, for example, a diazo dyestufi or an oxl 1a 1 leuco compound, the coloring penetrating into the gel regeneratedcellulose article to a more or less degree.

It is therefore an object of this invention to provide a method ofprinting which comprises locally dyeing or dyeing predetermined areas ofa wet pellic material, and preferably in the gel state, in accordancewith any desired indicia.

A specific object oi this invention is to provide a method of printingwhich comprises forming in situ a dyestufi, such as a diazo dyestuif oran oxi leuco base, in accordance with any desired indicia, on aregenerated cellulose article in the gel sta A further object of thisinvention is to provide permanently printed wet articles, such as thoseformed or pellicules of regenerated cellulose, the

printing being in accordance with any desired indicia and preferablyobtained by forming in situ a dyestufl which penetrates the regeneratedcellulose article.

Other objects will become apparent from the following description,appended claims and accompanying drawing wherein:

Figures 1 and 2 are perspective views of a cap and band of regeneratedcellulose printed in accordance with the instant invention.

print it. If the caps or bands are printed by .the

Figure 3 is a section through the printing showing the penetrationthereof into the regenerated cellulose.

Referring now to the drawing wherein like reference numerals designatelike parts, the reference numeral l designates a cap or band formed ofregenerated cellulose which is in the gel state and is provided withprinted indicia 2 of any suitable character. Referring now to Figure 3,it is to be noted that the printed indicia penetrates into the body ofthe article toa substantial degree.

The cap or band I may be prepared by immersing an appropriately shapedmandrel into a cellulosic solution, such as viscose, and, afterwithdrawing the same, coagulating and regenerating the adhering viscosesolution. Subsequently, the regenerated cellulose article is subjectedto the usual purifying operations, such as desulphuring and bleaching,and finally washed. At the end of these operations, the regeneratedcellulose article is in the gel condition and, in accordance with thisinvention, is printed as hereinafter more fully described.

The regenerated cellulose article, while in the gel state, is treated toremove the superficial moisture in any convenient manner, such as byblotting or passing through squeeze rolls. In this condition the gelregenerated cellulose is cally dyed in accordance with any desirableindicia. According to the broad phase of the invention, the printing isproduced by forming in situ a coloring material on local orpredetermined areas of the regenerated cellulose articles while in thegel state. This may be accomplished by treating the article while in thegel state successively with two substances which react to form acoloring agent as hereafter more fully explained. As an illustrativeexample of the process may be mentioned the formation in situ of a diazodye, an oxidized leuco compound, etc. on predetermined areas of thearticle in the gel state. It is of course to be understood that thefinal printing is of such a nature that it will effectively withstandthe substances to which the article is subjected in either the wet ordry state.

In carrying out the invention, caps or bands of regenerated cellulosewhile in the gel state and after the superficial moisture has beenremoved may be impregnated either completely or at predetermined areaswith either a diazo or a diazonium compound or a leuco base. A suitabledie or stamp bearing the required indicia or design moistened with asubstance which develops the diazo dye or oxidizes the leuco base isthen suitably applied, whereby the color is developed and the desiredprinting accomplished. The caps or bands are then washed to remove theexcess impregnating solution and treated to stabilize the resultingprinted indicia.

The preferred embodiments of this inventio contemplate the procedurewhich is the reverse to that set forth in the preceding paragraph. Inother words, the preferred procedure contemplates impregnating theregenerated cellulose article in the gel state with the developer or theoxidizer and then applying the diazo compound the regenerated cellulosearticle, while in the gel state and after the superficial moisture hasbeen removed, is treated so that the entire mass thereof or apredetermined area thereof is impregnated with a suitable naphtholsolution. A die or stamp bearing the required indicia or design is thenmoistened with a suitable solution containing a diazo compound ordiazonium salt and brought into contact with the previously impregnatedregenerated cellulose. The two substances react and produce a diazo dyeat the points of contact and the result is a localized dyeing orprinting. The regenerated cellulose article is then washed to remove,the naphthol solution which is in excess and finally treated with asuitable fixing agent, such as a dilute alkaline solution, for example,sodium carbonate, to effect complete removal of any residual naphtholand to fix the resulting dye.

If desired, the regenerated cellulose article in the gel state may beimpregnatedwith the solution of the diazo compound and the dye developedin situ by. subsequent treatment with the naphthol solution.

In another specific embodiment of the invention, the regeneratedcellulose article while in the gel state and after the superficialmoisture has been removed, is impregnated throughout or at predeterminedareas thereof with a solution of an oxidizing agent, for example, sodiumpersulphate. A printing die or stamp is moistened with a solution of areduced dye, commonly known as and referred to as a leuco base, andbrought in contact with the previously treated material. As the leucobase contacts with the oxidizing agent, its color is developed and theprinted indicia appears at the proper places on the regeneratedcellulose. Subsequently, articles are washed to remove the excessoxidizing agent and the product after stabilization and preservation isready for shipment.

As in the previous embodiment, the regenerated cellulose articles whilein the gel state may be impregnated with the leuco base and the colordeveloped by the application of the oxidizing agent.

It is obvious that the choice of printing solution components orreacting materials is entirely dependent on the color of the printingdesired.

The method of application of the impregnating component is variablewithout in any way affecting the scope of the invention. It may beapplied by passing the regenerated cellulose article through a solutionthereof and removing the excess thereof by .a squeeze roll, it may beapplied by a continuous wiper, or, alternatively, it may be applied topredetermined areas, where the final printing is to be' effected. Theprinting component applied to the die or stamp may be in the form of alimpid liquid or it may be in the form of a. soft or hard paste. Theonly requisite is that it be prevented from running either by adjustmentof the quantity applied or by the viscosity of the solution. It is of"course to be understood that the surface moisture must be removed fromthe article prior to printing, otherwise the printing might be blurredor otherwise defaced.

Though it is apparent that the printing may be effected on a plainregenerated cellulose article, it is to be understood that theregenerated cellulose article may be dyed either prior or subsequent tovthe printing, provided that this dye or dyeing operation does notinterfere with the printing process. Likewise, the regenerated celthewomen sohttoeh Psepeoe es ple ll.

' sohotmt Blue 3 eelt '(s diew of dienlsloline) till Distilledwotes -c.cloll Glycerin o e-.. 2.0

ton thoroug. Heel; w Printing is carried out as in l, the final colorbeing Tolue. I

. solute e A Nephthol AS-G (eto-ncet-o-thlh tilde) e: not Lhl}. llephthol (enillde of w. '1 23- nonhtholc ocld) do Sodium sulfonotedcostor oil 1 A oil) 9.6 Distilled water e. c.. aeoo 2li% coustic'sodo.(NoOH) c.c loo Prepare as for Solution A, Eimmpie l. Solution E thatBlue n salt (stabilized diazo of clienisidine)- 5.0 Distilled water c.c17.5

momma It is, of course, to he understood that these speciiic embodimentsare tor illustrative p v ondorenottobecofistniedaslimitinathe'soope oithe invention. 7 l

I i. J r a: E

sol A hominid). A8 (anllide oi? ,1

nophthoic acid) "ems" so Monopole oilo.'o @ll Distilled water -o.o3418.6 28% coustlo oodo (NeOE); c.o we

The nopthol AS end the monopole oil one rubbed together to tom e. pesto,o. ooztlon of! the woterjoeine: odd-ed it The meinder oi" thewoter loodoled to the to= eethen" with the osmotic soon eolution end the mixtosemilled too not it uteo.

someone me "no selt o to hem oi 1 chlozoo-t no=tolo)' w om..- toDistilled wet/er ..c.e.. loll Grin o c Ell the printima eppeets in e Moolot'.

Glycerin mil: thoroughly. I The painting operation is similar to that described in Example I, but the final color of the printing is black.

v1: A- LE IV Solution A llephthol AS-BG (2:5-dimethoxy enilide ofhetnhydrow-naphthoic 'acid) -gms 2.0 Denatured alcohol c. c- 3. 0 3o%Genetic w w! 2. 5 Boiling Water c.c 50.0 Cold water-eufilclenttomake c.c 100 The naphthol AS -HG end the denatured alcotool on role together toform 2. paste. The on eolution and boiling wetter are then added intheir tesneotive order, end otter complete solotion hos heen obtainedthe oold water-is odded to make the final r? vol Solution 3 eemet oosolt (etohilioed of %:5tZllel1l-e) mm 2.0 Distilled woteo c.c 7.63@lygmfln 0.8..- .5

' me ingredients ere thoroughly. The. printing; is to oleeeriheol in pieI. The eolox ls teal.

Em n w ll 7 he Wheet filettzi'lth; -m. "moon. 1 'Efiltleh no commo '3teegoeenth (ll co.) o .uert l Wateree "gallon" l ingredients ere edlooileol together;

to orozlnoe o moot-h oeete.

J Moowl tltlelteoerl.

PesteBS neellono 5% t otowlom eoehonete "pounds" it @nllozolte 6 (sodiumformaldehyde sultonnlote) mm 13% (llyceo' lee-lion" V Woter to makeneollonsn o The pesto end wtessium oorbonete ere heeted to ll'll" E. tilthe letter lino dissolved. The tore lo cooled to no" E l, when thesulilomte C and the, lycerin ere oddw. After the sullot'cite 6 lived,the M cooled heated to l7 I until the letter has dissolved,

when the ew is cooled to 14W F. and the sulfointe C and glycerin added.When solution is cete the w water is added-to make 3 gallons. This pasteprinting paste it it should be necessary.

is cooled and sufiicient i for reduction is used for dilution 0! thestandard In the application of this example to the printing ofregenerated cellulose caps or hands in the gel state, the standardprinting paste is applied to the stamp or die and the latter thenapplied in the desired position on the cap or band. The development ofthe dye may proceed in either of two ways. The printed cap may be setaside for an aging period of several hours at room temperature, and thenoxidation completed by washing in cold running water, or a weak chromebathmay be substituted for the water oxidation. As analternative methodfor printing, the caps or bandsin the gel state may be saturated with asuitable oxidizing agent, such as sodium persulphate, and under theseconditions the printing should develop immediately on the application ofthe die or stamp, whereupon a washing operation and fixing operationcomparable to ,that

' used in conjunction with the diazo dyes would complete the operation.The final color is blue.

Articles of regenerated cellulose printed in accordance with theprocedures outlined in the foregoing examples may be purified by washingin running water for several hours after which they may be treated iorminutes in a hot 3 solution of sodium,carbonate in water. A second waterwashing of 3-4 hours may be given and the articles are finally packed inthe preservation or shipping solution which maintains them in a tilswollen condition until ready for use.

In the foregoing, the invention is described in connection with thetreatment of regenerated cellulose articles in ,Ithe gel state. Byregenerated cellulose articles are meant articles formed of a pelliculeof regenerated cellulose, such as caps, bands, sheets, films, tubes,etc. By the term "gel as used in this specification is meant the statein which the regenerated cellulose articles are obtained before anydrying action has taken place. Though the preferred embodiment of theinvention relates to the printing of articles formed of a pellicularmaterial while in the gel state, the invention is also applicable forprinting dry articles formed of pellicular materials which have beenwetted and swollen prior to the printing operation. I

It is to be understood that the printing is not restricted to anyprecise method or means, but may be accomplished with the aid of anysuitable manual or mechanical means. For instance, regenerated cellulosetubing in the gel state may be passed through a rotary printing machineor a gang type printingmachine, whereby a number of prints are madesimultaneously and the tubing subsequently cut to the desired lengths.Similarly, in the manufacture of continuous sheeting of regeneratedcellulose, the printing r'nay be applied before the gel regeneratedcelluloseiilm reaches the final drying stepand preferably in anoperation combined with the method of producing the same. The finaldried product will then bear periodically recurring groups of separateand distinct indicia or in the form of a continuous design.

Though the invention has been described spe-. ciiically in conn ion withregenerated cellulose articles in the wet and/or gel state, theprinciples thereof are equally applicable to the treating of articles inthe wet and/or gel state, such as caps and bands, formed of certainresinous materials which are capable of being coagulated from solutionsand remain in a wet and/or gel state, cellulose acetate, gelatin, etc.and which are maintained in the wet and/or gel state'until used.

Since it is obvious that various modifications may be made in thespecific details hereinbefore described without departing from thespirit of the invention, the invention is not restricted thereto exceptas defined in the appended claims.

I claim:

1. A method which comprises treating predetermined areas of an articleformed of a pellicular material while in the water wet state to producein situ a substantially permanent color which penetrates into the bodyof the article and is in accordance with the desired indicia.

2. A method which comprises treating predetermined areas of an articleformed of a pellicular material while in the water wet state to producein situ a substantially permanent dyestufi which penetrates into thebody of the article and is in accordance with the desired indicia.

3. A method which comprises treating predetermined areas of an articleformed of a pellicular material while in the water wet state to producein situ a diazo dye which penetrates into the body of the article and isin accordance with the desired indicia.

4. A method which comprises treating predetermined areas of an articleformed of a pellicular materialwhile in the water wet state to producein situ an oxidized leuco compound which penetrates into the body of thearticle and is in accordance with thedesired indicia.

5. A method which comprises treating predetermined areas of an articleformed of a regenerated cellulose pellicule while in the water wet stateto produce in situ a substantially permanent color which penetrates intothe body of the article, and is in accordance with the desired indicia.

6. A method which comprises treating predetermined areas of an articleformed of a regenerated cellulose pellicule while in the water wet stateto produce insitu'a' substantially permanent dyestufi which penetratesinto the body of the article, and is in accordance with the desiredindicia.

7. A method which comprises treating predetermined areas of an articleformed of a regenerated cellulose pellicule while in the water wet stateto produce in situ .a diaz dye which penetrates into the body of thearticle, and is in accordance with the desired indicia.

8. A method which comprises treating predetermined areas of an articleformed of a rewet state to producein situ an oxidized leuco compoundwhich penetrates into the body of the article, and is in accordance withthe desired indicia.- I

9. A method which comprises producing an appropriately shaped articleformed of a purifled regenerated cellulose pellicule in the water 'wetstate, removingthe surface moisture from said article, and thereaftertreating predetermined areas of said article while in the wet state toproduce in, situ a substantially permanentcolor which penetrates intothe body of said article, and is in accordance with the desired in-.

generated cellulose pellicule while in the water appropriately shapedarticle formed of a purifled regenerated cellulose pellicule in thewater wet state, removing the surface moisture from said article, andthereafter treating predetermined areas of said article while in the wetstate to produce in situ a diazo dye which penetrates into the body ofsaid article, and is in accordance with the desired indicla.

12. A method which comprises producing an appropriately shaped articleformed .01 a purified regenerated cellulose pellicule in the water wetstate, removing the surface moisture from said article, and thereaftertreating predetermined areas of said article while in the wet state toproduce in situ an oxidized leuco compound which penetrates into thebody of said article, and is in accordance with the desired indicia.

13. A protective covering comprising a permanently printed,appropriately shaped, wet pellicule, the indlcia constituting theprinting being formed of a color which is produced in situ,substantially permanent, and penetrates into the said pellicule, saidcovering being adapt ed, when placed upon the article to be covered, toshrink by loss of moisture and firmly attach itself to said article.

i l. A protective covering comprising a permanently printed,appropriately shaped, wet pellicule, the indicia constituting theprinting being formed of a dyestuff which is developed in situ,substantially permanent, and penetrates into the said pellicule, saidcovering being adapted, when placed upon the article to be covered, toshrink by loss of moisture and firmly attach itself to said article.

15. A protective covering comprising a permanently printed,appropriately shaped, wet pellicule of regenerated cellulose, theindicia constituting the printing being formed of a color which isproduced in situ, substantially permanent, and penetrates into the saidpellicule, said covering being adapted, when placed upon the article tobe covered, to shrink by loss of moisture and iirmly attach itself tosaid article.

16. A protective covering comprising a permanently printed,appropriately shaped, wet pellicule or regenerated cellulose, theindicia constituting the printing being formed of a dye stuit which isproduced in situ, substantially permanent, and penetrates into the saidpellicule,

said covering being adapted, when placed upon the article to be covered,to shrink by loss of moisture and firmly attach itself to said article.

neatly printed, appropriately shaped, wet pe1li-' cule of regeneratedcellulose, the indicia constituting the printing being formed of anomdized leuco compound which is produced in situ, substantiallypermanent, andpenetrates into the said pellicule, said covering beingadapted when placed upon the article to be covered to shrink by lossofmoisture and firmly attach itself to said article.

19. A method which comprises treating predetermined areas of an articleformed of a pellicular material while in the gel state to produce insitu a substantially permanent .dyestufi which penetrates into the bodyof the article and is in accordance with the desired indicia.

20. A method which comprises treating predetermined areas of an articleformed of a regenerated cellulose pellicule while in the gel state toproduce in situ a substantially permanent dyestufi which penetrates intothe body of the article, and is in accordance with the desired in'dicia.

21. A method which comprises treating prede-. termined areas of anarticle formed of a, regenerated cellulose pellicule while in the gelstate to produce in situ a diazo dye which penetrates into the body ofthe article, and is in accordance with the'desired indicial 22. A methodwhich comprises treating predetermined areas of an article formed of aregenerated cellulose pellicule while in the gel state to produce iiisitu an oxidized leuco compound which penetrates into the body of thearticle, and is in accordance with the desired indicia.

23. A protective covering comprising a perma-, nently printed,appropriately shaped, pellicular material in the gel state, the indiciaconstituting the printing being formed of a color which is prodficed insitu, substantially permanent, and

penetrates into the said pellicule, said covering being adapted, whenplaced upon the article to be covered, to shrink by loss of moisture andfirmly attach itself to said article.

24. A protective covering comprising a per nently printed, appropriatelyshaped, pellicular material in the gel state, the indicia constitutingthe printing being formed of a dyestufi which is developed in situ,substantially permanent, and penetrates into the said pellicule, saidcovering being adapted, when placed upon the article to be covered,to 1. r i by loss of moisture and ly attach itself to said article.

25. A protective covering comprising a permanently printed,appropriately shaped pellicule of regeneratedcellulose in the gel state,the indicia constituting the printing being formed of a diazo dyestufiwhich is produced in situ, substantially permanent, and penetrates intothe said pellicule,

said covering being adapted, when placed upon the article to be covered,to shrink by loss oi moisture and firmly attach itself to-said article.

26, A protective covering comprising a perma nently printed,appropriately shaped'pel licule of regenerated cellulose in the gelstate, the indicia constituting the printing being formed of an oxidized leuco compound which is produced in situ,

, bstarrtially permanent, and penetrates into the said pellicule, saidcovering being adapted, when aced upon the article to be covered, to tby loss of moisture and firmly. attach itself to sd article.

